|Publication number||US5032310 A|
|Application number||US 07/543,050|
|Publication date||Jul 16, 1991|
|Filing date||Jun 22, 1990|
|Priority date||Aug 16, 1983|
|Publication number||07543050, 543050, US 5032310 A, US 5032310A, US-A-5032310, US5032310 A, US5032310A|
|Inventors||Robert H. McIntosh, Sr.|
|Original Assignee||Interface, Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (110), Non-Patent Citations (40), Referenced by (6), Classifications (34), Legal Events (5)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This is a continuation-in-part application of U.S. Ser. No. 080,787, filed Sept. 3, 1987, now abandoned, which is a continuation-in-part of U.S. Ser. No. 047,561, filed on Apr. 27, 1987, now U.S. Pat. No. 4,935,232; 781,710 filed on Oct. 2, 1985, now abandoned; 635,728 filed on July 30, 1984, now abandoned; application Ser. No. 658,695 filed on Oct. 9, 1984, now abandoned; application Ser. No. 713,445 filed on Mar. 19, 1985, now abandoned; application Ser. No. 736,652 filed on May 21, 1985, now U.S. Pat. No. 4,647,601; application Ser. No. 744,916 filed on June 13, 1985, now abandoned; and application Ser. No. 744,730 filed on June 13, 1985, now abandoned; all of which are continuations-in-part of application Ser. No. 570,952 filed Mar. 8, 1984, now U.S. Pat. No. 4,608,289 which in turn was a continuation of application Ser. No. 523,734 filed Aug. 16, 1983, now abandoned, which was a continuation of application Ser. No. 226,006 filed Jan. 19, 1981, now abandoned, which was a continuation of application Ser. No. 930,879 filed Aug. 4, 1978, also now abandoned.
This invention relates microbiocidal cleansing and disinfecting formulations and methods for their preparation and use.
Bacteria, fungi, viruses, algae and other microorganisms are always present in our environment. Such microorganisms are frequently an essential part of ecological systems, industrial processes, and healthy human and animal bodily functions, such as digestion. In other instances, however, microorganisms are highly undesirable because they can cause the illness or death of humans and animals. They can also create odors or damage or destroy a wide variety of materials.
The species and numbers of microorganisms present are dependent on a number of factors, including the availability of nutrients and moisture, the humidity and the temperature of the local environment. Certain bacteria are capable of remaining viable in a dormant state on floors or on objects for long periods of time until they are deposited in the proper media for growth.
Nutrients for microorganisms are typically abundant. For example, dried skin, discarded foods, plants, animal wastes, synthetic and natural materials like plastic coatings and objects, wood, paper, and natural fibers are all excellent nutrient media for many types of microorganisms, including potentially damaging organisms. Microorganisms can degrade useful materials as they feed on them.
A major difficulty in health care facilities, such as hospitals and nursing homes, is the spread of dangerous infectious diseases by microorganisms. The problem is exacerbated in these facilities because many of the patients are in a weakened condition due to illness. A microorganism that would not be a major threat to a healthy person could be fatal to a patient with a diminished capacity to defend himself from infection. Potentially dangerous microorganisms are spread in health care facilities and elsewhere by a variety of means, including on the clothes or skin of health care personnel. The transfer is prevented by cleaning skin or clothes with a nonmicrobiocidal soap or detergent.
Clothing that is used during exercise is particularly susceptible to the accumulation of harmful microorganisms. If these microorganisms are not killed or inhibited, they can cause extensive damage to the fabric, offensive odors and infections. Conventional detergents are often ineffective in killing or removing the microorganisms.
It has proved difficult to develop a microbiocidal cleanser or disinfectant that is effective in controlling the growth of a wide variety of harmful microorganisms and is, at the same time, safe for use around human beings and animals. One of the sources of difficulty in the control of potentially harmful microorganisms is the extreme variability of response of various microorganisms to conventional microbiocidal agents. For example, bacteria, which are classified as procaryotes, can be killed or inhibited by many different types of antibiotics. However, the same antibiotics that are effective against procaryotic organisms are usually ineffective against eucaryotic microorganisms, such as fungi and yeasts.
Even within the family of Bacteriaceae, there are two broad categories of bacteria, Gram-positive and Gram-negative bacteria. These classifications are based on the ability of bacteria to absorb certain vital stains (Gram-negative bacteria absorb positively charged stains and Gram-positive bacteria absorb negatively charged stains). The two groups of bacteria generally also respond differently to the same microbiocidal agent. An antimicrobial agent that is effective against one type of bacteria may not be effective against the other type.
One method of inhibiting the growth of both eucaryotes and procaryotes or both Gram-negative and Gram-positive bacteria is to combine two or more microbiocidal inhibitors that are designed to inhibit or kill a specific organism or class of organisms. However, various problems arise when introducing two or more additives into a material such as a detergent. The multiple additives may alter the physical properties of the detergent. In addition, the multiple components must be tested to insure compatibility and continued microbiocidal effectiveness when combined with the detergent. It is not uncommon for the combination of microbiocidal additives to initially have effective inhibiting or killing properties for both Gram-positive and Gram-negative organisms. However, with the passage of time, one or the other of the inhibiting additives can deteriorate and lose its effectiveness while the other inhibiting additive remains effective. In addition, one additive may have an unexpected inhibitory effect on the other additive. Further, the requirement of adding two or more additives can become prohibitively expensive.
Accordingly, there is a need, both in industry and in the home, for a safe and effective microbiocidal cleanser or disinfectant that can be used on a wide variety of substances.
Therefore, it is an object of the present invention to provide a microbiocidal cleanser or disinfectant that will kill or inhibit a wide variety of microorganisms.
It is another object of the present invention to provide a microbiocidal cleanser or disinfectant that is safe for use around humans and animals.
It is a further object of the present invention to provide a microbiocidal cleanser or disinfectant that can deposit a microbiocidal agent on the object cleaned as a means to impart microbiocidal activity to the object.
The invention described herein is a microbiocidal cleansing or disinfecting solution, and a method for its preparation, that includes an effective amount of a phosphoric acid ester of the structure ##STR2## wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, and neopentyl and X is selected from the group consisting of Group IA metals, Group IIA metals, transition metals, and HNR1 R2 R3 +, wherein R1 and R2 are alkyl groups of from 4 to 18 carbon atoms or a hydroxyalkyl group of 1 to 18 carbon atoms, and R3 is an alkyl group of from 8 to 18 carbon atoms, and wherein when R is hydrogen, X is di-(2-hydroxyethyl)cocoamine. These phosphoric acid derivatives are highly water soluble and especially useful in an aqueous disinfectant or detergent.
The microbiocidal cleansing or disinfecting agent can kill or inhibit the growth of many types of bacteria, fungi, viruses, yeasts and other destructive or disease-producing microorganisms that can be found on a surface. The phosphoric acid ester is effective against both Gram-positive bacteria, such as Staphylococcus aureus, and Gram-negative bacteria, such as Pseudomonas aeruginosa. The phosphoric acid ester is also capable of killing the causative organism of Legionnaires' disease, Legionella pneumophilia.
By adjusting the concentration of the reactants in the preparation of the alkyl phosphoric acid ester, bactericidal activity can be selected. For example, the phosphoric acid ester can be prepared so that it is effective primarily against Gram-negative bacteria, against Gram-positive bacteria or both.
The phosphoric acid ester can be added to water to provide a microbiocidal disinfectant solution or can be added to a conventional detergent to provide a microbiocidal cleansing solution. The detergents that can be used in the cleansing solution include, but are not limited to, linear alkyl sulfonates, alkyl benzene sulfonates, and metal salts of long chain fatty acids.
The effective amount of phosphoric acid ester to be used in the cleanser or detergent will vary based on the job to be done. For example, a light duty disinfectant may include from 0.005 to 0.01% (50 to 100 ppm) phosphoric acid ester, whereas a heavy duty cleanser might include from 15 to 70% phosphoric acid ester.
As used herein, the term "microorganism" refers to any organism that cannot easily be seen with the naked eye and includes bacteria, molds, yeasts, fungi, algae and viruses. The terms "antimicrobial" and "microbiocidal" describe the killing or inhibition of microorganisms. The term "bactericidal" describes the killing or inhibition of the growth of bacteria. "Fungicidal" describes the killing of, as well as the inhibition of the growth of, fungi, yeasts and molds. The term "viricidal" is used to describe the inactivation or inhibition of viruses. The term "cleansing agent" includes any substance capable of cleaning, emulsifying, or removing unwanted material from a surface. The term "detergent" describes any substance or product which is capable of dislodging, removing, or dispersing solid and liquid soils from a surface being cleansed. The term "detergent" also includes soaps comprising metal salts of long chain fatty acids. The term "disinfectant" includes any liquid that is capable of killing or inhibiting microorganisms.
The present invention is a microbiocidal cleansing or disinfecting solution that includes an effective amount of a phosphoric acid ester of the formula: ##STR3## wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, and neopentyl and X is selected from the group consisting of Group IA metals, Group IIA metals, transition metals, and HNR1 R2 R3 +, wherein R1 and R2 are alkyl groups of from 4 to 18 carbon atoms or a hydroxyalkyl groups of 1 to 18 carbon atoms, and R3 is an alkyl group of from 8 to 18 carbon atoms, and wherein when R is hydrogen, X is di-(2-hydroxyethyl)cocoamine. It is believed that at least one free hydroxyl group on the phosphate group is important for substantial microbiocidal activity. In a preferred embodiment, R is ethyl, R1 and R2 are C2 H4 OH, and R3 is C12 H25.
When used as described herein, the solutions are capable of killing or inhibiting the growth of a wide variety of microorganisms including fungi, yeasts, viruses, algae and bacteria. For example, the cleansing or disinfecting solution inhibits the growth of the following representative Gram-negative and Gram-positive bacteria: Sarcina lutea, Staphylococcus species, Pseudomonas aeruginosa, Pseudomonas cepacia, Escherichia coli, Escherichia communior, Bacillus subtilis, Klebsiella species, Salmonella species, Legionella pneumophilia, Enterobacter aerogenes and Streptococcus species. The cleanser or disinfectant inhibits the growth of the following representative fungi and yeasts: Candida albicans, Trichophyton metagrophytes, Trichophyton rubrum, Trichophyton interdigitale and Aspergillus niger. The cleanser or disinfectant also inactivates Herpes simplex virus. These microorganisms are often present in hospitals and other health care facilities.
The cleanser or disinfectant can be used to impart long term microbiocidal protection to a fiber or fabric. The phosphoric acid ester is mixed with a liquid such as water or other solvent or dispersant and then applied to the fiber by dipping, spraying or washing the fiber or fabric in the solution. When the water or solvent is removed, some of the phosphoric acid ester remains in the fiber or fabric. Thereafter, microorganisms that come into contact with the fiber or fabric will be killed or inhibited. For this application, the concentration of phosphoric acid ester in the water or other solvent or dispersant is preferably between 0.01% and 30% by weight. The preferred concentration of the ester in the dispersant or solvent is between 0.1% and 10% by weight, and most preferred concentration is between 0.5% and 6% by weight. Suitable solvents that can be used to apply the phosphoric acid ester include, but are not limited to, benzene, toluene, xylene, and hexane. Examples of the type of fiber or fabric products contemplated include, but are not limited to, surgical gauze, padding on wound dressings, mattress covers, crib covers, bassinet covers, sailboat sails, tents, draw sheets, cubicle curtains, hair brushes, fabric wall covering, shower curtains, bath mats, athletic clothing, shirts, socks, shorts, pants, shoes and the like, and hospital clothing such as examination robes, physicians coats and nurses uniforms.
The phosphoric acid ester solution can be added to the water in cooling towers to kill or inhibit the growth of the pathogen that causes Legionaire's disease, Legionella pneumophilia.
Monoalkyl phosphoric acid can be produced by reacting P2 O5 with an alcohol, or by any other method known to those skilled in the art. Alternatively, the monoalkyl phosphoric acid ca be purchased commercially.
One mole of P2 O5 reacted with three moles of alcohol produces a mixture predominately of monoalkyl phosphoric acid along with some dialkyl phosphoric acid. In the preferred embodiment, the reaction is carried out at a temperature ranging from 60° to 120° C., and typically at the reflux temperature of the alcohol.
The dialkyl phosphoric acid is a stronger base than the monoalkyl phosphoric acid, and therefore, preferentially reacts with a base added to the product mixture to form a salt. For example, 1.0 m of monoalkyl phosphoric acid and 1.0 m of dialkyl phosphoric acid reacted with 1.3 moles of an amine produces approximately 1.0 m of ammonium dialkyl phosphate, 0.3 m of ammonium monoalkyl phosphoric acid and 0.7 m of monoalkyl phosphoric acid.
In the preferred embodiment, the monoalkyl phosphoric acid is partially neutralized with an organic substituted amine to produce an ammonium salt of an alkyl phosphoric acid.
The alkyl phosphoric acid can instead be partially neutralized with a Group I metal, Group II metal, or transition metal. For example, the alkyl phosphoric acid can be partially neutralized with sodium hydroxide or potassium hydroxide, to produce the sodium or potassium salt of the alkyl phosphoric acid, respectively. Alternatively, the alkyl phosphoric acid can be partially neutralized with magnesium acetate or zinc acetate, to produce the corresponding salts. Since magnesium and zinc are in a +2 oxidation state, each zinc or magnesium ion will coordinate with two molecules of alkyl phosphoric acid.
Selection of the positive ion affects biocidal activity, principally the anti-Gram-negative bactericidal activity, although the alkyl phosphoric acid appears to be the primary source of biocidal activity The biocidal activity is also a function of the relative ratio of mono- to dialkyl substituted phosphoric acid ester.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to the fullest extent. The following specific embodiments, are, therefore, to be construed as merely illustrative, and not limiting of the remainder of the disclosure. Percentage of composition is by weight unless otherwise indicated.
To 3 m of ethanol is sloWly added 1 m of P2 O5 with vigorous stirring at a reaction temperature of 60° C. The reaction is complete in about two hours. The progress of reaction is monitored by titrating the acid produced with a solution of base. The reaction products include mono-(ethyl)phosphoric acid and di-(ethyl)phosphoric acid.
1.3 Moles of di-(hydroxyethyl)-cocoamine is slowly added to 2.0 moles of the reaction products of Example I (assuming an equal product mixture of mono- and dialkyl phosphoric acid) until the pH is between approximately 2 and 5 (preferably between 3.2 and 3.8) in a 75% ethanol water solution. The reaction is carried out in a temperature range from approximately 60° C. to 120° C. (preferably 100° C.) until the reaction is complete.
The reaction product contains: ##STR4## wherein R=ethyl, R1 and R2 are C2 H4 OH, and R3 is C12 H25.
The zinc salt of the ethylphosphoric acid mixture is prepared by mixing 32 g of ethylphosphoric acid (as prepared in Example I or purchased commercially) with 15 g of zinc acetate (Zn(OCO2 CH3)2 *2H2 O). These reagents are mixed and then the acetic acid is removed by vacuum distillation.
The magnesium salt of the ethylphosphoric acid mixture is prepared by reacting 20 g of magnesium acetate (Mg(OCO2 CH3)2.4H2 O) with 32 g of ethylphosphoric acid. The reagents are mixed and warmed, and the acetic acid is then stripped off by vacuum distillation.
The microbiocidal activity of the phosphoric acid ester or its partially neutralized derivative can be evaluated as follows. Petri dishes are prepared using appropriate nutrient agar as a food source for the microorganism to be tested. The microorganism is seeded into the agar by well known methods. A hole 6 mm in diameter and 5 mm deep is cut into the agar. The test compound (0.05 ml) is placed in the hole and the inoculated petri dish is incubated for 24 hours at 37° C. After the 24 hour incubation period, the relative susceptibility of the test organism to the phosphoric acid derivative is demonstrated by a clear zone of growth inhibition around the test solution. As the phosphoric acid ester diffuses through the agar medium from the hole, its concentration progressively diminishes to a point that it no longer inhibits the test organism. The area of suppressed microbial growth, the zone of inhibition, is a function of the biocidal activity of the compound and its ability to diffuse through the medium.
After the 24 hour incubation period, each plate is examined. The diameters of the complete inhibition zones are measured using reflected light and a measuring device such as a sliding caliper, a ruler, or a template prepared for this purpose and held on the bottom of the plate. The end point, measured to the nearest millimeter, is the point at which no visible growth can be detected with the unaided eye, minus the diameter of the test drop or sample.
The biocidal activity of three mixtures, 91% mono-(2-ethylhexyl)phosphoric acid and 9% di-(2-ethylhexyl)phosphoric acid ester; 55% mono-(2-ethylhexyl)phosphoric acid ester and 45% di(2-ethylhexyl)phosphoric acid ester; and 95% di-(2-ethylhexyl) phosphoric acid ester and 5% mono-(2-ethylhexyl)phosphoric acid ester against Gram-positive Staphylococcus aureus and Gram-negative Pseudomonas aeruginosa were tested using the above-described assay. Each test was performed at least 6 times, and the results averaged. The results are provided in Table 1.
TABLE 1______________________________________Zone of Inhibition in mm2 91% 95%Organism Mono-ester Mixture Di-Ester______________________________________S. aureus 352 240 148P. aeruginosa 319 148 28______________________________________
As shown in Table 1, the monoalkyl phosphoric acid ester has significantly greater activity than the dialkyl phosphoric acid ester against these organisms.
Two moles of the product of Example I (using 2-ethylhexyl alcohol in place of ethanol) were neutralized with between 0.5 moles and 3.0 moles of di-(2-hydroxyethyl)cocoamine using the procedure of Example II. The microbiocidal activity of the various mixtures against S. aureus and P. aeruginosa were then determined using the above-described assay. The results are provided in Table 2.
TABLE 2______________________________________Molar Ratio S. aureus P. aeruginosaof reactants Area of Inhibition measured in mm2______________________________________A. Product from 3848 706 Example IB. 0.5 moles cocoaminea 1520 614C. 1.0 moles cocoaminea 907 706D. 1.3 moles cocoaminea 452 1257E. 1.5 moles cocoaminea 452 38F. 2.0 moles cocoaminea 452 13G. 2.5 moles cocoaminea 201 13H. 3.0 moles cocoaminea 153 0I. Cocoamine only 153 0______________________________________ a Moles of cocoamine reacted with two moles of the product from Example II.
As shown in Table 2, sample A, which is a mixture of unneutralized mono and dialkylphosphoric acid, has excellent microbiocidal activity against both the Gram positive Staphylococcus aureus and the Gram negative Pseudomonas aeruginosa. The reaction product from Example I retains its microbiocidal activity against both of these organisms even when reacted with up to 2 moles of di-(2-hydroxyethyl)cocoamine. When two moles of the reaction product from Example I is reacted with more than 2 moles of the cocoamine, the microbiocidal activity is diminished. Although not wanting to be bound to the following mechanism, it is considered that the reduction in microbiocidal activity above 2 moles of the cocoamine is due to the neutralization of the free hydroxyl group of the phosphate group. Three moles of cocoamine neutralize all of the hydroxyl groups in the two moles of reaction product mixture, severely minimizing the microbiocidal activity. As shown, the cocoamine itself has slight microbiocidal activity against the Gram positive Staphylococcus aureus.
As illustrated above, the spectrum of activity of the phosphoric acid ester can be manipulated by proper choice of the amount of amine used. For example, the pure, unneutralized phosphoric acid ester is more active against the Gram-positive organism than the Gram-negative organism. The phosphoric acid ester neutralized with 1.3 mole of amine is more active against the Gram-negative organism than the Gram-positive organism.
The zinc and magnesium salts of ethylphosphoric acid prepared as described in Examples 3 and 4, respectively, are evaluated for biocidal activity using above-described procedure. Both compounds produce clear zones of inhibition against S. aureus and Pseudomonas aeruginosa.
A microbiocidal cleanser is prepared as described in Example 9. The microbiocidal cleanser is then heated to 85° C. Cotton fabric is added to the cleanser and retained there for a period of 15 minutes. The fabric is then rinsed in water at 40° C., removed, and dried.
Square samples of the treated fabric of approximately 400 mm2 are cut and placed on agar plates which have previously been inoculated with Staphylococcus aureus and Pseudomonas aeruginosa. The plates are then incubated at 35° C. for 24 hours.
After the incubation, neither Staphylococcus aureus nor Pseudomonas aeruginosa are found to be present in or on the squares. Microscopic examination shows a zone of inhibition around the individual threads.
The phosphoric acid ester can be added to water or other solvents to provide a disinfectant formulation or can be added to a conventional detergent to provide a microbiocidal cleansing agent. The detergents that can be used in the present invention include, but are not limited to, linear alkyl sulfonates, alkyl benzene sulfonates, and metal salts of long chain fatty acids.
The phosphoric acid ester is mixed with water or other desired solvent at any desired concentration, preferably between 0.01 and 70% by weight. The effective amount of the phosphoric acid derivative in the cleanser or disinfectant will be determined by its intended use. For example, a solution containing from approximately 0.005 to 0.01% (50 to 100 parts per million (ppm)) of the ester provides an excellent disinfectant formulation for light duty, for example, mopping and cleaning of hard surfaces such as vinyl walls, floors, counters and table tops.
A strong biocidal cleansing formulation such as that required for a surgical scrub, is prepared by mixing the phosphoric acid ester with a conventional detergent at a concentration of between approximately 15% and 70% by weight.
An aqueous microbiocidal cleanser is prepared by mixing 0.05% by weight of the di-(2-hydroxyethyl)cocoamine salt of ethylphosphoric acid prepared as in Example 2 with an aqueous detergent.
A microbiocidal cleansing agent can be prepared by (i) neutralizing phosphoric acid with between approximately 1 and 2 moles of di - (2-hydroxyethyl) cocoamine; and (ii) mixing the mixture from step (i) at a concentration of between approximately 0.01% and 70% by weight with a detergent.
A disinfectant is prepared by mixing 0.01% by weight of the di-(2-hydroxyethyl)cocoamine salt of ethylphosphoric acid prepared as in Example 2 with water.
A dry free-flowing mixture comprising the microbiocidal cleansing agent was prepared by mixing 0.3 grams of the product of Example 2 with 138.5 grams of "All" detergent as purchased over the counter. One gram of the cleansing agent mixture was then placed in the center of inoculated petri dishes and incubated for 24 hours at 37° C. Control plates were also prepared using one gram samples of the detergent without phosphoric acid derivative. After this period of incubation, each plate was examined and the diameters of the inhibition zones were measured. The results are shown in Table 3.
______________________________________ Zone of Inhibition Zone of Inhibition in mm2 for detergent and in mm2 for detergentOrganism alkyl phosphate derivative (Control)______________________________________S. aureus 2827 706P. aeruginosa 1017 113______________________________________
As shown in Table 3, the detergent along exhibits some microbiocidal activity probably because of the presence of sodium hypochlorite which would be washed out of fabrics during the rinsing process. However, the detergent plus phosphoric acid ester demonstrates a significant increase in microbiocidal activity over the detergent alone.
Modifications and variations of the present invention, microbiocidal cleansing and disinfecting formulations and preparation thereof, will be obvious to those skilled in the art from the foregoing detailed description. Such modifications and variations are intended to come within the scope of the appended claims.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2202134 *||Oct 4, 1938||May 28, 1940||Cottrell C B & Sons Co||Web perfecting rotary press|
|US2272668 *||Nov 10, 1939||Feb 10, 1942||Reichhold Chemicals Inc||Partial phosphoric esters and process for preparing same|
|US2337424 *||Mar 23, 1943||Dec 21, 1943||Stoner Mudge Inc||Coating composition for metals|
|US2541088 *||Dec 5, 1946||Feb 13, 1951||Burton T Bush Inc||Process for preparing n-alkyl substituted n, n-beta, beta'-dialkanolamines|
|US2552325 *||Feb 24, 1947||May 8, 1951||Monsanto Chemicals||Diethyl octyl phosphates|
|US2592564 *||May 22, 1948||Apr 15, 1952||Standard Oil Co||Asphalt cutback containing an aliphatic phosphoric acid ester|
|US2676122 *||Jan 9, 1951||Apr 20, 1954||Du Pont||Antistatic treatment of hydrophobic fiber|
|US2756175 *||Jul 2, 1952||Jul 24, 1956||Sun Chemical Corp||Fungicidal compositions comprising copper-8-quinolinolate solubilized with heavy metal salts of alkyl phosphoric acid esters|
|US2831782 *||May 21, 1954||Apr 22, 1958||Dow Chemical Co||Lubricants for coating and working light metals|
|US2872351 *||Nov 15, 1954||Feb 3, 1959||Bohme Fettchemie Gmbh||Compositions for and methods of finishing textile materials|
|US2891878 *||Apr 11, 1955||Jun 23, 1959||American Cyanamid Co||Antistatic polymeric coatings|
|US2922738 *||May 27, 1955||Jan 26, 1960||Ethyl Corp||Fungicidal compositions|
|US2934490 *||Jan 30, 1957||Apr 26, 1960||Exxon Research Engineering Co||Two-pass hydroforming|
|US2936288 *||Aug 22, 1956||May 10, 1960||Composition|
|US2960529 *||Oct 29, 1959||Nov 15, 1960||Eastman Kodak Co||Process for preparing neutral phosphates|
|US2970081 *||Jul 31, 1958||Jan 31, 1961||Monsanto Chemicals||Mycobacteriostats|
|US2976186 *||Nov 27, 1957||Mar 21, 1961||Eastman Kodak Co||Treated textile fiber|
|US2997454 *||May 18, 1959||Aug 22, 1961||Argus Chem||Polyvinyl chloride stabilizer combinations of phosphorus acid with triphosphites andheavy metal salts|
|US3247134 *||Jul 9, 1962||Apr 19, 1966||Owens Corning Fiberglass Corp||Fire retardant cellular polyurethane compositions containing an organic phosphate amine salt|
|US3279986 *||May 12, 1965||Oct 18, 1966||Herculite Protective Fab||Bacteriostatic material|
|US3280131 *||Feb 10, 1964||Oct 18, 1966||Millmaster Onyx Corp||Quaternary ammonium salts of organophosphorus acids|
|US3294775 *||Feb 11, 1964||Dec 27, 1966||Wasco Lab Inc||Reaction products of stabilized rosin amine and organic acid phosphate esters|
|US3308488 *||May 3, 1965||Mar 14, 1967||Schoonman Richard J||Bacteriostatic drawsheet|
|US3312623 *||Dec 23, 1963||Apr 4, 1967||Monsanto Co||Antiseptic detergent compositions|
|US3364192 *||Jul 27, 1964||Jan 16, 1968||Pfizer & Co C||Antistatic polymer compositions containing ammonium phosphates|
|US3404140 *||Sep 9, 1964||Oct 1, 1968||Toyo Rayon Co Ltd||Shaped article of polyolefin composition having improved dyeability containing metalcompounds and a process for dyeing the same|
|US3428713 *||Jan 13, 1965||Feb 18, 1969||Du Pont||Alkanol amine salts of phosphates|
|US3475204 *||Sep 18, 1967||Oct 28, 1969||Du Pont||Polyester tire cord lubricant|
|US3498969 *||Oct 11, 1967||Mar 3, 1970||Swift & Co||Phosphonate amine polyol compounds and a process for preparing same|
|US3527726 *||Jul 17, 1968||Sep 8, 1970||Atlantic Richfield Co||Water-soluble ammonium or amine salts of phosphate esters of styrene-maleic anhydride copolymer - polyalkylene glycol esters|
|US3577515 *||Mar 4, 1968||May 4, 1971||Pennwalt Corp||Encapsulation by interfacial polycondensation|
|US3620453 *||Sep 24, 1969||Nov 16, 1971||Gancberg Abraam||Shaped article with insecticidal properties|
|US3639594 *||Jun 5, 1967||Feb 1, 1972||Prodotti Antibiotici Spa||Pharmaceutical compositions containing 6-phosphogluconic acid and salts thereof|
|US3641226 *||Nov 24, 1969||Feb 8, 1972||Atomic Energy Commission||Method for purification of di-(2-ethyl-hexyl) phosphoric acid|
|US3671304 *||Apr 23, 1970||Jun 20, 1972||Arkansas Co Inc||Process for flameproofing and resultant product|
|US3705235 *||Apr 30, 1971||Dec 5, 1972||Predicted Environments Inc||Sanitizing plastic material|
|US3708573 *||Feb 27, 1970||Jan 2, 1973||Kumiai Chemical Industry Co||Agricultural and horticultural granule formulation and methods for preparing the same and for using thereof|
|US3714256 *||May 26, 1970||Jan 30, 1973||Kendall & Co||Diallyl and dimethallyl alkyl lipophilic benzyl ammonium halides|
|US3758283 *||Sep 24, 1971||Sep 11, 1973||Du Pont||Conductivity additive for liquid hydrocarbons|
|US3762415 *||Mar 6, 1968||Oct 2, 1973||Maxine B Money||Anti-bacterial menses absorbing pads|
|US3769377 *||May 20, 1970||Oct 30, 1973||Chevron Res||Dialkylphosphorylbicyclo(eta.2.0)alkanes|
|US3776806 *||May 24, 1972||Dec 4, 1973||Allied Chem||Filament comprising a polymer blend of polyester and polyamide containing an organic phosphorus compound|
|US3793408 *||Jan 28, 1972||Feb 19, 1974||Atomic Energy Commission||Method for the purification of bis (2-ethyl-hexyl) phosphoric acid|
|US3819656 *||Nov 6, 1970||Jun 25, 1974||Gulf Research Development Co||Uniform mixtures of quaternary ammonium salt isomers|
|US3832464 *||Sep 13, 1971||Aug 27, 1974||Ciba Geigy Ag||Pesticidal compositions containing phosphoric acid esters and elemental sulphur|
|US3873648 *||Jul 7, 1972||Mar 25, 1975||Ugine Kuhlmann||Method for separating mixtures of orthophosphoric esters|
|US3885000 *||Jun 27, 1973||May 20, 1975||Ciba Geigy Ag||S,S-dialkyl-o-and s-alkenyl phosphites and phosphates|
|US3888978 *||Aug 9, 1973||Jun 10, 1975||Hoechst Ag||Certain phosphorus acid esters as disinfectants|
|US3896101 *||Nov 16, 1971||Jul 22, 1975||Askew Anthony B||Additive for plastic materials|
|US3897491 *||Jun 10, 1971||Jul 29, 1975||Stauffer Chemical Co||Process for preparing alkyl or aryl phosphorus halides and mixed isomers thereof|
|US3897521 *||Jun 27, 1973||Jul 29, 1975||Ciba Geigy Ag||S,S-Dialkyl-O-alkylthioalkyl phosphites and phosphates|
|US3919410 *||Jun 10, 1974||Nov 11, 1975||Askew Anthony B||Sanitizing plastic material|
|US3920836 *||Dec 21, 1973||Nov 18, 1975||Askew Anthony B||Sanitizing plastic material|
|US3925442 *||Mar 18, 1974||Dec 9, 1975||Kendall & Co||Monomeric emulsion stabilizers|
|US3928563 *||Apr 22, 1974||Dec 23, 1975||Askew Anthony B||Self-sanitizing film former|
|US3932612 *||Jun 15, 1973||Jan 13, 1976||Bayer Aktiengesellschaft||Insecticidal compositions for sustained release of 0,0-dimethyl-0-(2,2-dichlorovinyl) phosphate|
|US3933947 *||Aug 8, 1973||Jan 20, 1976||Bayer Aktiengesellschaft||O-ethyl-S-propyl-S-benzyl-phosphorodithiolates|
|US3959556 *||Jul 2, 1974||May 25, 1976||Morrison Willard L||Antimicrobial blended yarns and fabrics comprised of naturally occurring fibers|
|US3972243 *||Jul 23, 1973||Aug 3, 1976||Sun Research And Development Co.||Traction drive with a traction fluid containing gem-structured polar organo compound|
|US3979307 *||Sep 10, 1973||Sep 7, 1976||Texaco Inc.||Fabric softener composition|
|US3991187 *||May 6, 1974||Nov 9, 1976||Aktiebolaget Leo||Medicinal compositions and methods of use involving phosphoric acid esters|
|US4004001 *||Sep 2, 1975||Jan 18, 1977||Stauffer Chemical Company||Phosphorus containing insecticide activators|
|US4006204 *||Apr 30, 1975||Feb 1, 1977||Nelson Research & Development Company||Phosphoric acid diesters|
|US4024324 *||Dec 9, 1975||May 17, 1977||Uop Inc.||Novel polyolefin composition of matter|
|US4025583 *||Jan 12, 1976||May 24, 1977||Texaco Inc.||Amine adducts of ethyl oleyl acid orthophosphate|
|US4039636 *||Jun 28, 1973||Aug 2, 1977||The Dow Chemical Company||Magnesium dialkyl phosphates and their preparation|
|US4071552 *||May 19, 1976||Jan 31, 1978||Ayerst Mckenna And Harrison Ltd.||Aryloxy aminobutanols, their preparation and use thereof|
|US4083860 *||Mar 26, 1976||Apr 11, 1978||Th. Goldschmidt Ag||Metal compounds of monoesters of phosphoric acid|
|US4094970 *||Aug 12, 1976||Jun 13, 1978||Bayer Aktiengesellschaft||Elastomeric polyurethane-based articles having an insecticidal depot gas action|
|US4107292 *||Feb 16, 1977||Aug 15, 1978||Akzona Incorporated||Stable water dispersions of encapsulated parathion|
|US4110504 *||Jun 15, 1976||Aug 29, 1978||Anthony B. Askew||Self-sanitizing carpet construction composition|
|US4119724 *||Apr 13, 1977||Oct 10, 1978||Pepro||Fungicidal compositions containing phosphorous acid and derivatives thereof|
|US4139616 *||Dec 10, 1974||Feb 13, 1979||Pepro||Fungicidal compositions based on phosphorous acid esters and salts thereof|
|US4152421 *||Sep 30, 1977||May 1, 1979||Kao Soap Co., Ltd.||Dentifice composition|
|US4209398 *||Jul 3, 1978||Jun 24, 1980||Kurita Water Industries Ltd.||Water treating process|
|US4235733 *||Jul 11, 1979||Nov 25, 1980||Kao Soap Co., Ltd.||Antibacterial soap containing trichlorohydroxy diphenyl ether bactericide and an organic phosphoric ester as a stabilizer therefor|
|US4255259 *||Sep 18, 1979||Mar 10, 1981||Chemed Corporation||Scale inhibition|
|US4259078 *||Jun 5, 1979||Mar 31, 1981||Hoechst Aktiengesellschaft||Heat-stable quaternary ammonium compounds for fiber lubricating|
|US4272395 *||Dec 20, 1979||Jun 9, 1981||Lever Brothers Company||Germicidal compositions|
|US4276418 *||Jan 28, 1980||Jun 30, 1981||Imperial Chemical Industries Limited||Process for the purification of esters of phosphorus thioacids|
|US4289634 *||Jul 25, 1979||Sep 15, 1981||Chevron Research Company||Deposit control additives and fuel and lube oil compositions containing them|
|US4343853 *||Mar 6, 1980||Aug 10, 1982||Morrison Willard L||Antimicrobially treated fabric construction|
|US4361611 *||Dec 10, 1980||Nov 30, 1982||Ciba-Geigy Corporation||Process for providing synthetic textile fabrics with an antistatic finish|
|US4363663 *||Apr 6, 1981||Dec 14, 1982||Hill Nicholas J||Antimicrobial solution|
|US4401712 *||Jan 3, 1983||Aug 30, 1983||Tultex Corporation||Antimicrobial non-woven fabric|
|US4432833 *||Feb 25, 1982||Feb 21, 1984||Kimberly-Clark Corporation||Pulp containing hydrophilic debonder and process for its application|
|US4442095 *||Dec 27, 1982||Apr 10, 1984||Merck & Co., Inc.||N-[(5-Halo-2,6-(substituted)pyrazinyl)methylene]amine antimicrobial compounds, compositions and use|
|US4442096 *||Dec 27, 1982||Apr 10, 1984||Merck & Co., Inc.||2-(Substituted)amino-3-cyano-5-halo-6-(substituted)-pyrazine antimicrobial compounds, compositions and use|
|US4560599 *||Jan 28, 1985||Dec 24, 1985||Marquette University||Assembling multilayers of polymerizable surfactant on a surface of a solid material|
|US4598006 *||May 2, 1985||Jul 1, 1986||Hercules Incorporated||Method for impregnating a thermoplastic polymer|
|US4647601 *||May 21, 1985||Mar 3, 1987||Interface Research Corporation||Self-sanitizing epoxy resins and preparation thereof|
|US4661477 *||Sep 29, 1982||Apr 28, 1987||Borsodi Vegyi Kombinat||Phosphoric acid monoester salts, process for their preparation, and fungicidal compositions containing them as active ingredient|
|US4770694 *||Mar 10, 1982||Sep 13, 1988||Kao Soap Co., Ltd.||Aqueous biocide suspension|
|CA1162356A *||May 12, 1982||Feb 21, 1984||Mitsubishi Burlington||Antimicrobial carpet and preparation thereof|
|CH617854A5||Title not available|
|DE1228031B *||Jun 11, 1965||Nov 3, 1966||Hoechst Ag||Bakterizide|
|DE2530584A1 *||Jul 9, 1975||Jan 20, 1977||Henkel & Cie Gmbh||Desinfizierende mittel auf basis von quartaeren ammoniumverbindungen|
|DE3014765A1 *||Apr 17, 1980||Oct 29, 1981||Henkel Kgaa||Amino hydrohalide antimicrobials - for use as surface disinfectants with a long lasting effect|
|DE3039437A1 *||Oct 18, 1980||May 27, 1982||Bosch Gmbh Robert||Sterilising packaging material with conc. ortho-phosphoric acid - pref. by passing through phosphoric acid bath and then removing residue|
|DE3248708C2||Dec 31, 1982||May 26, 1988||Chemmar Associates, Inc., Greensboro, N.C., Us||Title not available|
|EP0018492A1 *||Mar 21, 1980||Nov 12, 1980||Hoechst Aktiengesellschaft||Aqueous disinfectant solution|
|EP0035375A1 *||Feb 26, 1981||Sep 9, 1981||Takeda Chemical Industries, Ltd.||Carbamic acid esters, their production and use|
|FR2237311B1||Title not available|
|GB1036578A||Title not available|
|GB1302894A||Title not available|
|GB2042574B||Title not available|
|GB2131029B||Title not available|
|JP53081577U||Title not available|
|SU840218A1||Title not available|
|SU1122664A1||Title not available|
|1||*||Derivatives of Anhydro Acids, 348.|
|2||*||Gialkdi et al., Chem. Abstracts 43, 6363a (1949) (Farm sci. e tec. 4, 166 175).|
|3||Gialkdi et al., Chem. Abstracts 43, 6363a (1949) (Farm sci. e tec. 4, 166-175).|
|4||*||Hall et al., Chem. Abstracts, 80, 123000 (1973) ASLE Trans. 16(4), 291 296.|
|5||Hall et al., Chem. Abstracts, 80, 123000 (1973) ASLE Trans. 16(4), 291-296.|
|6||*||Honaker et al., J. Inorg. Nucl. Chem., 39, 1703 1704, (1977).|
|7||Honaker et al., J. Inorg. Nucl. Chem., 39, 1703-1704, (1977).|
|8||*||J. Inorg. Nucl. Chem., 38, 2127 2129, (1976).|
|9||J. Inorg. Nucl. Chem., 38, 2127-2129, (1976).|
|10||*||J. Perka et al., Tenside Detergents, 15, 295 298, (1978)6.|
|11||J. Perka et al., Tenside Detergents, 15, 295-298, (1978)6.|
|12||*||Keil et al., Chem. Abstracts 76, 101944k (1972) Ger. Offen. 2,030,256.|
|13||*||Lin Chin Ann et al., Surfactant Chemistry, 85 88 (1978).|
|14||Lin Chin-Ann et al., Surfactant Chemistry, 85-88 (1978).|
|15||*||Matsui et al., Chem. Abstracts, 82, 141561, (1974) (JP 74 24,806).|
|16||*||McCoy Microbiology of Cooling Water 94 95 (Chemical Pub. Co., NY 1980).|
|17||McCoy Microbiology of Cooling Water 94-95 (Chemical Pub. Co., NY 1980).|
|18||*||Nakamura, Journal of Radioanalytical Chemistry, 44, 37 47, (1978).|
|19||Nakamura, Journal of Radioanalytical Chemistry, 44, 37-47, (1978).|
|20||*||Nakamura, Journal of Radioanalytical Chemistry, 52(2), 343 354, (1979).|
|21||Nakamura, Journal of Radioanalytical Chemistry, 52(2), 343-354, (1979).|
|22||*||Ogasawara et al., Chem. Abstracts 81, 107078f (1974) (U.S. Pat. No. 3,799,904).|
|23||*||Partridge et al., J. Inorg. Nucl. Chem., 31, 2587 2589, (1969).|
|24||Partridge et al., J. Inorg. Nucl. Chem., 31, 2587-2589, (1969).|
|25||*||Sorbe et al., Quim. Apl. Jorn. Com. Esp. Deterg., 11th, pp. 415 430 (1980).|
|26||Sorbe et al., Quim. Apl. Jorn. Com. Esp. Deterg., 11th, pp. 415-430 (1980).|
|27||*||Sudakova et al., Chem. Abstracts, 76, 56711v (1969) (USSR 229,879).|
|28||*||Surfactant Science Series, vol. 7, Anionic Surfactant, 504 507 and 545 567 (1976).|
|29||Surfactant Science Series, vol. 7, Anionic Surfactant, 504-507 and 545-567 (1976).|
|30||*||Tachimori et al., Journal of Radioanalytical Chemistry, 67(2), 329 337, (1981).|
|31||Tachimori et al., Journal of Radioanalytical Chemistry, 67(2), 329-337, (1981).|
|32||*||Tak Chemicals Ltd. 1580026 (Jun. 1977).|
|33||Takehiko Fujimoto, "Introduction in New Surfactant", pp. 295-297, (1974).|
|34||*||Takehiko Fujimoto, Introduction in New Surfactant , pp. 295 297, (1974).|
|35||*||Useful Agrochemicals, 408 411.|
|36||Useful Agrochemicals, 408-411.|
|37||Yoshihira Koda et al., "The Synthesis of Surfactant and the use thereof", pp. 96-99 and 436-447, (1977).|
|38||*||Yoshihira Koda et al., The Synthesis of Surfactant and the use thereof , pp. 96 99 and 436 447, (1977).|
|39||*||Yuan et al., Phosphorus and Sulphur, vol. 18, 323 326 (1983).|
|40||Yuan et al., Phosphorus and Sulphur, vol. 18, 323-326 (1983).|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US5587407 *||Jun 6, 1995||Dec 24, 1996||Interface, Inc.||Biocidal polymeric coating for heat exchanger coils|
|US5635192||Jun 6, 1995||Jun 3, 1997||Interface, Inc.||Biocidal polymeric coating for heat exchanger coils|
|US5639464||Jun 6, 1995||Jun 17, 1997||Interface, Inc.||Biocidal polymeric coating for heat exchanger coils|
|US6063335 *||Feb 20, 1998||May 16, 2000||Henkel Corporation||Method for disinfecting surfaces|
|US20050177957 *||Jan 7, 2003||Aug 18, 2005||Long Jack W.||Topical treatment for carpet and textiles and topically treated carpet and textile products|
|EP1157642A1 *||May 23, 2000||Nov 28, 2001||International Bedding cvba||Bedding system|
|U.S. Classification||510/382, 510/383, 514/75, 514/76|
|International Classification||A01N33/08, A01N33/04, D06M13/292, A01N57/14, C08K5/521, C11D3/48, C11D3/36, C08K5/00, D06M16/00, A01N57/12|
|Cooperative Classification||C11D3/362, C08K5/521, A01N33/04, A01N33/08, D06M16/00, C11D3/48, A01N57/14, C08K5/0058, A01N57/12, D06M13/292|
|European Classification||C11D3/48, C08K5/521, C08K5/00P7, A01N57/12, D06M13/292, C11D3/36C, A01N57/14, A01N33/04, D06M16/00, A01N33/08|
|Apr 15, 1991||AS||Assignment|
Owner name: INTERFACE, INC., ATLANTA, GEORGIA 30339 A CORP. OF
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:MC INTOSH, ROBERT H. SR.;REEL/FRAME:005665/0702
Effective date: 19910409
|Sep 29, 1994||FPAY||Fee payment|
Year of fee payment: 4
|Jan 15, 1999||FPAY||Fee payment|
Year of fee payment: 8
|Jan 15, 2003||FPAY||Fee payment|
Year of fee payment: 12
|Jan 9, 2004||AS||Assignment|
Owner name: WACHOVIA BANK, NATIONAL ASSOCIATION, GEORGIA
Free format text: SECURITY INTEREST;ASSIGNOR:INTERFACE, INC.;REEL/FRAME:014910/0414
Effective date: 20031218
Owner name: WACHOVIA BANK, NATIONAL ASSOCIATION,GEORGIA
Free format text: SECURITY INTEREST;ASSIGNOR:INTERFACE, INC.;REEL/FRAME:014910/0414
Effective date: 20031218